Preparation of esters of acids of phosphorus



Patented Dec. 6 1949 UNITED STATES PATENT Q-FFICE PREPARATION OF ESTERSF ACIDS 0F" PHQSPHORUS No llbrawing'. Application June 29, L945 SerialNo. 602,4;

3 Claims.

This invention relates to. the preparation of hitherto unknown esters ofthe, acids of phos-.- phorus and more particularly to the preparationof.phosphated and phosphited compounds de-. rived from unsaturated acids.

This invention has for its object to provide a process for producingcertain new chemical compounds which are esters of the acids ofphosphorus. A further object is, to provide new pliesphatedandphosphited compounds which are derived from blown unsaturatedcarboxylic acids.v A still further object is. to. provide improvedphosphated and phosuhited compounds having exceptional usefulness assurface-ac iv agents, ting, washing, and disbursing agents, and as lu-:brioating, anti-static and conditioning agents for textile v yarns,particularly those composed of or containing cellulose acetate and,related cellulose derivatives. Other objects will appear hereinafter.

These objects are accomplished by the following invention, which isbased upon the unexpected discovery that if certain unsaturated carboxyic acids containing the group C=C H H are heated and then blown with,air 0 O y until an appreciable increase in specific gravity of thecompounds. occurs,- such compoundswill react with acids of phosphorus;such as. phosa pho us, hyp phosphorous. phosphoric, thiephosphoric, andthe various pyroand polyphose phorous and phosphoric acids. This is amost unusual phenomenon when it is taken into consideration thatcompounds containing the group C=C H H such as oleic acid, butyl oleate,oleyl alcohol, carbitol oleate, ethylene glycol dioleate, and butylricinoleate, do not add acids of phosphorus, such as phosphorous andphosphoric acids when mixed and heated therewith.

While we do not confine ourselves to any specific theory or explanationof the mechanism of the reaction involved when the unsaturated compoundsare blown as above described, the reaction may be as follows:

The reaction between the phosphorus acid and the structure resultingfrom the blowing operation may be represented conventionally as follows:

It. will thus. be, seen,- that; the phosphate or phosphito group, adds;to the carbon chain at the po.-.

sition. or in lly c p e before w y n unsat rated linka e- In. en al). te u satura ed cqm n ted or. b owiners h as c ic acid. i acid, in oleicacid, ace yiated ricin e c ac d, oleic. a id ester 03% ricinoleic.acid,..un e.c acid, enydrceenated- (2m sehaeio ac d. an he a i s fromoils such as sosaheanl. co on. sard n menhadia. peanut, and the like,are heated from 50 to 200 C; (Ede-H551 (1. pr ferred); and o ox en, ipassed in unt l a product hav n th d r pronerti s is. obtained: Whe the.unsa urated come is blewnthe iod ne. valu -t ls, whfl he pecificgravity, reiraetive-index,.-a y va ue and sanonifica icnxcquiralenrise-i On ki ed. in. the art can by f-ollowinazt enreeress o he alcoveconstan s, de ermine when. to; step. b ow n the uasaturated compound so.aste obta n a product that will readily react with-an acid ofphosphorus. Any or the -ens. or i.c a ids: at phosphorus may bemplcyedforphosphatine 0.1: phQs-phitine the blown compounds n accordancwith our Example 1 g. of oleic acid is blown at 1- until the specificgravity has increased ODS-units. Then 30 g. phosphoric acid are addedand the mixture heated with stirring on a steam bath for 10 hours. Theexcess acid is removed with cold water or cold aqueous salt solutions.The brownish viscous product is water soluble. For phosphoric acidsubstitute phosphorous acid, pyrophosphoric 3 acid, tetraphosphoric acidor any other poly acid of phosphorous.

, maple z 100 g. of erucic acid are blown as above and reacted withphosphorous acid as in Example 1. The product is soluble in water.

Example 3 100 g. of ricinoleic acid are blown and reacted as in 1 with60 g. of tetraphosphorous acid. The product is soluble in water.

Example 4 100 g. of acetylated ricinoleic acid are blown as in 1 andphosphated as above with 60 g. of phosphoric acid. The product is watersoluble.

Example 5 100 g. of the oleate of ricinoleic acid are blown as in 1 andphosphated as above with 70 g. of phosphoric acid. The product is watersoluble.

Example 6 100 g. of the acids from soyabean oil are blown as in 1 andphosphated as above. The product is water soluble.

While we have found it convenient to illustrate our invention byreference to procedures involving the blowing of certain specificunsaturated carboxylic acids, it will be evident that many modificationsin such procedures may be made within the scope of our invention. Ingeneral, it may be said that, irrespective of the particular acid dealtwith, the blowing operation may be carried out in a manner analogous tothat which is customarily employed in the blowing of various oils, fats,and waxes.

The blown and phosphated or phosphited compounds of our invention havemany valuable applications in industry. For example, they may beemployed as surface-active agents, wetting, washing and disbursingagents. We have also found them to have outstanding properties whenemployed as lubricating anti-static and conditioning agents fortextile'yarns, particularly those composed of or containing celluloseacetate and related cellulose derivatives.

1 The preparation of novel esters of an acid of phosphorus is disclosedand claimed in our copending applications Serial No. 602,412, filed June4 29, 1945, issued as Patent No. 2,466,393, and Serial No. 602,415,filed June 29, 1945, now abandoned.

What we claim is: 1. The process of producing an ester of an acid ofphosphorus which comprises blowing an unsaturated acid having theformula:

wherein R represents an unsaturated hydrocarbon chain containing from 17to 21 carbon atoms in which the unsaturation is limited to olefinicunsaturation, at from to 200 C., until an appreciable increase inspecific gravity occurs, and thereafter treating the blown acid with anacid of phosphorus selected from the group consisting of phosphoric andphosphorous acids.

2. The process of producing an ester of an acid of phosphorus whichcomprises blowing oleic acid, at from 50 to 200 C., until an appreciableincrease in specific gravity occurs, and thereafter treating the blownacid with an acid of phosphorus selected from the group consisting ofphosphoric and phosphorous acids.

3. The process of producing an ester of an acid of phosphorus whichcomprises blowing erucic acid, at from 50 to 200 0., until anappreciable increase in specific gravity occurs, and thereafter treatingthe blown acid with an acid of phosphorus selected from the groupconsisting of phosphoric and phosphorous acids.

JOSEPH B. DICKEY. JAMES G. McNALLY.

REFERENCES CITED The following references are of record in the file ofthis patent:

UNITED STATES PATENTS Number Name Date 1,936,533 Albrecht Nov. 2, 19332,185,967 Priestler Jan. 2, 1940 2,252,479 Beyer Aug. 12, 1941 2,260,819Balassa Oct. 28, 1941 2,345,734 Dickey et al Apr. 4, 1944 OTHERREFERENCES Fats and Oils, Kirschenbauer (1944), page 20, Reinhold Pub.Co.

Industrial Oil and Fat Products by Bailey, Interscience Publ. (1945) pp.42-43.

